Ionic Dimethacrylates for Antimicrobial and Remineralizing Dental Composites.

Two ionic dimethacrylates (IDMA1 and IDMA2) intended for utilization in multifunctional, antibacterial and remineralizing dental resins and composites were synthesized by nucleophilic substitution reactions. Crude IDMAs were purified by multi-step extraction from ethanol-diethyl ether-hexane solvent system. Their structures were validated by nuclear magnetic resonance and mass spectrometry. As evidenced by the water contact angle measurements ((63.2-65.5)0), IDMAs did not affect the wettability of urethane dimethacrylate (UDMA)- based copolymers (average contact angle ((60.8±5.1)0).The attained degrees of vinyl conversion increased from 88.1% (no-IDMA control) up to 93.0% (IDMA2 series). Flexural strength (FS) of copolymers was reduced from 94.8 MPa (control) to (68.9-71.8) MPa (IDMA counterparts) independent of monomer type and/or its concentration. This reduction in FS should not disqualify IDMAs from consideration as viable antibacterial agents in multifunctional restoratives. Tested at concentrations exceeding the expected leachability of unreacted monomers from cured copolymers and/or composites, IDMAs had no deleterious effect on viability and/or metabolic activity of fibroblasts. The remineralization potential of amorphous calcium phosphate IDMA/UDMA composites was confirmed by calcium and phosphate ion release kinetic experiments. Results of this study warrant in-depth biological, physicochemical, mechanical and antibacterial assessments of IDMA resins and composites to identify prototype(s) suitable for clinical testing.

Polymerization shrinkage and stress development in amorphous calcium phosphate/urethane dimethacrylate polymeric composites.

This study explores how substituting a new high molecular mass oligomeric poly(ethylene glycol) extended urethane dimethacrylate (PEG-U) for 2-hydroxyethyl methacrylate (HEMA) in photo-activated urethane dimethacrylate (UDMA) resins affects degree of vinyl conversion (DC), polymerization shrinkage (PS), stress development (PSSD) and biaxial flexure strength (BFS) of their amorphous calcium phosphate (ACP) composites. The composites were prepared from four types of resins (UDMA, PEG-U, UDMA/HEMA and UDMA/PEG-U) and zirconia-hybridized ACP. Introducing PEG-U improved DC while not adversely affecting PS, PSSD and the BFS of composites. This improvement in DC is attributed to the long, more flexible structure between the vinyl groups of PEG-U and its higher molecular mass compared to poly(HEMA). The results imply that PEG-U has the potential to serve as an alternative to HEMA in dental and other biomedical applications.

Selected physicochemical properties of the experimental endodontic sealer.

This study explores water sorption, hygroscopic expansion, mechanical strength and ion release from the experimental amorphous calcium phosphate (ACP) composites formulated for application as endodontic sealers. Light-cure (LC) and dual-cure (DC; combined light and chemical cure) resins comprised urethane dimethacrylate (UDMA), 2-hydroxyethyl methacrylate (HEMA), methacryloyloxyethyl phthalate (MEP) and a high molecular mass oligomeric co-monomer, poly(ethyleneglycol)-extended UDMA (PEG-U) (designated UPHM resin). To fabricate composites, a mass fraction of 60% UPHM resin was blended with a mass fraction of 40% as-made (am-) or ground (g-) ACP. Glass-filled composites were used as controls. Both DC and LC ACP UPHM composites exhibited relatively high levels of water sorption accompanied by a significant hygroscopic expansion. The latter may potentially be useful to offset high polymerization stresses that develop in these materials. Ion release profiles of the experimental materials confirmed their potential for regeneration of mineral-deficient tooth structures. Their moderate to low mechanical strength after 3 months of aqueous immersion did not diminish the enthusiasm for the proposed use as endodontic sealers. For that application, DC g-ACP composites appear to be the most adequate, but micro-leakage and quantitative leachability studies are needed to fully establish their suitability.

AMORPHOUS CALCIUM PHOSPHATE COMPOSITES AND THEIR EFFECT ON COMPOSITE-ADHESIVE-DENTIN BONDING.

This study evaluates the bond strength and related properties of photo-polymerizable, remineralizing amorphous calcium phosphate (ACP) polymeric composite-adhesive systems to dentin after various periods of aqueous aging at 37 °C. An experimental ACP base and lining composite was made from a photo-activated resin comprising 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxyethyl methacrylate (HEMA) and zirconyl dimethacrylate (ZrDMA); designated BTHZ. An experimental orthodontic composite was formulated from a photo-activated resin comprising ethoxylated bisphenol A dimethacrylate (EBPADMA), TEGDMA, HEMA and methacryloxyethyl phthalate (MEP); designated ETHM. In both composite series three fillers were compared: 1) freshly precipitated zirconium-modified ACP freshly precipitated (as-prepared Zr-ACP), 2) milled Zr-ACP and 3) an ion-leachable fluoride glass. In addition to the shear bond strength (SBS), work to fracture and failure modes of the orthodontic composites were determined. The SBS of the base and lining ACP composites appeared unaffected by filler type or immersion time. In the orthodontic ACP composite series, milled ACP composites showed initial mechanical advantages over as-prepared ACP composites, and produced higher incidence of a failure mode consistent with stronger adhesion. After six months of aqueous exposure, 80 % of specimens failed at the dentin-primer interface, with a 42 % overall reduction in bond strength. BTHZ and ETHM based ACP composites are potentially effective anti-demineralizing-remineralizing agents with possible clinical utility as protective base-liners and orthodontic cements, respectively. The analysis of the bond strength and failure modalities suggests that milled ACP composites may offer greater potential in clinical applications.

In vitro remineralization of enamel by polymeric amorphous calcium phosphate composite: quantitative microradiographic study.

OBJECTIVE: This study explores the efficacy of an experimental orthodontic amorphous calcium phosphate (ACP) composite to remineralize in vitro subsurface enamel lesions microradiographically similar to those seen in early caries. METHODS: Lesions were artificially created in extracted human molars. Single tooth sections a minimum of 120microm thick were cut and individually placed in holders exposing only the carious enamel surface. The exposed surfaces were either left untreated (control) or coated with a 1mm thick layer of the experimental ACP composite (mass fraction 40% zirconia-hybridized ACP and 60% photo-activated resin), or a commercial fluoride-releasing orthodontic cement. The composite-coated sections were then photo-cured and microradiographic images were taken of all three groups of specimens before the treatment. Specimens were then cyclically immersed in demineralizing and remineralizing solutions for 1 month at 37 degrees C to simulate the pH changes occurring in the oral environment. Microradiographs of all specimens were taken before and after treatment. RESULTS: Quantitative digital image analysis of matched areas from the contact microradiographs taken before and after treatment indicated higher mineral recovery with ACP composites compared to the commercial orthodontic F-releasing cement (14.4% vs. 4.3%, respectively), while the control specimens showed an average of 55.4% further demineralization. SIGNIFICANCE: Experimental ACP composite efficiently established mineral ion transfer throughout the body of the lesions and restored the mineral lost due to acid attack. It can be considered a useful adjuvant for the control of caries in orthodontic applications.

Degree of vinyl conversion, polymerization shrinkage and stress development in experimental endodontic composite.

This study explores degree of vinyl conversion (DVC), polymerization shrinkage (PS) and shrinkage stress (PSS) of the experimental amorphous calcium phosphate (ACP) composites intended for use as an endodontic sealer. Light-cure (LC), chemical cure (CC) or dual-cure (DC; combined light and chemical cure) resins comprised urethane dimethacrylate (UDMA), 2-hydroxyethyl methacrylate (HEMA), methacryloyloxyethyl phthalate (MEP) and a high molecular mass oligomeric co-monomer, poly(ethyleneglycol)-extended UDMA (PEG-U) (designated UPHM resin). To fabricate composites, a mass fraction of 60 % UPHM resin was blended with a mass fraction of 40 % as-made (am-ACP) or ground ACP (g-ACP). DVC values of copolymer (unfilled UPHM resin) and composite specimens were determined by infrared spectroscopy. Glass-filled composites were used as controls. PS and PSS of composites were determined by dilatometry and tensometry, respectively. LC copolymers attained extraordinary high DVC values at 24 h post-cure (95.7 %), compared to CC (52 %) and DC (79.3 %) copolymer specimens. While the DVC values of LC and DC am-ACP composites were reduced between 5 and 10 %, DVC values of DC g-ACP composites increased almost 8 % compared to the corresponding copolymers. High DVC attained in LC composites was, expectedly, accompanied with high PS values (on average 7 vol%). However, PSS developed in LC and especially DC composites did not exceed PSS values seen in other UDMA-based composites. Based on this initial evaluation, it is concluded that, DC, g-ACP filled UPHM composite shows promise as an endodontic sealer. However, further physicochemical evaluations, including water sorption, mechanical stability and ion release as well as a leachability studies need to be performed before this experimental material is tested for cellular responses and, eventually recommended for clinical utility.

Light-cured dimethacrylate-based resins and their composites: comparative study of mechanical strength, water sorption and ion release.

This study explored how resin type affects selected physicochemical properties of complex methacrylate copolymers and their amorphous calcium phosphate (ACP)-filled and glass-filled composites. Two series of photo-polymerizable resin matrices were formulated employing 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (Bis-GMA) or an ethoxylated bisphenol A dimethacrylate (EBPADMA) as the base monomer, Unfilled copolymers and composites filled with a mass fraction with 40 %, 35 % and 30 %, respectively, of ACP or the un-silanized glass were assessed for biaxial flexure strength (BFS), water sorption (WS) and mineral ion release upon immersion in HEPES-buffered saline solution for up to six months. Substituting EBPADMA for Bis-GMA significantly reduced the WS while only marginally affected the BFS of both dry and wet copolymers. Independent of the filler level, both dry and wet ACP composites formulated with either BTHM or ETHM resins were mechanically weaker than the corresponding copolymers. The BFS of ACP composite specimens after 1 month in saline did not further decrease with further aqueous exposure. The BFS of glass-filled composites decreased with the increased level of the glass filler and the time of aqueous exposure. After 6 months of immersion, the BFS of glass-filled BTHM and ETHM composites, respectively, remained 58 % and 41 % higher than the BFS of the corresponding ACP composites. Ion release data indicated that a minimum mass fraction of 35 % ACP was required to attain the desired solution supersaturation with respect to hydroxyapatite for both the BTHM and ETHM derived composites.

ILLUMINATING THE ROLE OF AGGLOMERATES ON CRITICAL PHYSICOCHEMICAL PROPERTIES OF AMORPHOUS CALCIUM PHOSPHATE COMPOSITES.

Water sorption (WS), mechanical strength, and ion release of polymeric composites formulated with 40 % as-made or milled amorphous calcium phosphate (ACP) are compared after 1, 2 and 3 months of aqueous exposure. Ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate comprised the resin. The WS (mass %) peaked at 3 months. WS of as-made ACP composites was significantly higher than WS of milled ACP composites and copolymers. Both composite groups experienced decreases in biaxial flexural strength (BFS) with water aging, with milled ACP composites retaining a significantly higher BFS throughout immersion. Ion release was moderately reduced in milled ACP composites, though they remained superior to as-made ACP composites due to significantly lower WS and higher BFS after prolonged aqueous exposure.

Amorphous Calcium Phosphate Based Composites: Effect of Surfactants and Poly(ethylene oxide) on Filler and Composite Properties.

The uncontrolled aggregation of amorphous calcium phosphate (ACP) particulate fillers and their uneven distribution within polymer matrices can have adverse effects on the properties of ACP composites. In this paper we assessed the influence of non-ionic and anionic surfactants and poly(ethylene oxide) (PEO) introduced during the preparation of ACP on the particle size distribution and compositional properties of ACP. In addition, the mechanical strength of polymeric composites utilizing such fillers with a photo-activated binary methacrylate resin was evaluated. Zirconia-hybridized ACP (Zr-ACP) filler and its corresponding composite served as controls for this study. Surfactant- and PEO-ACPs had an average water content of 16.8 % by mass. Introduction of the anionic surfactant reduced the median particle diameter about 45 % (4.1 µm vs. 7.4 µm for the Zr-ACP control). In the presence of PEO, however, the d(m) increased to 14.1 µm. There was no improvement in the biaxial flexure strength (BFS) in any of the dry composite specimens prepared with the surfactant- and/or PEO-ACPs compared to those formulated with Zr-ACP. The BFS of wet composite specimens decreased by 50 % or more after a month-long exposure to saline solutions. Other types of surfactants and/or polymers as well as alternative surface modification protocols need to be explored for their potential to provide better dispersion of ACP into the matrix resin and better mechanical performance ACP composites.

Effect of Chemical Structure and Composition of the Resin Phase on Vinyl Conversion of Amorphous Calcium Phosphate-filled Composites.

The objective of this study was to elucidate the effect of chemical structure and composition of the polymer matrix on the degree of vinyl conversion (DC) of copolymers (unfilled resins) and their amorphous calcium phosphate (ACP) composites attained upon photo-polymerization. The DC can also be an indicator of the relative potential of these polymeric materials to leach out into the oral environment un-reacted monomers that could adversely affect their biocompatibility. The following resins were examined: 1) 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (1:1 mass ratio; BT resin) combined with hydroxyethyl methacrylate (HEMA; BTH resin) and with HEMA and zirconyl dimethacrylate (BTHZ resin), 2) urethane dimethacrylate (UDMA)/HEMA resins, and 3) pyromellitic glycerol dimethacrylate (PMGDMA)/TEGDMA (PT resin). To make composite specimens, resins were mixed with a mass fraction of 40 % zirconia-hybridized ACP. Copolymers and their composites were evaluated by near infra-red spectroscopy for DC after 1 d and 28 d post-cure at 23 °C. Inclusion of HEMA into the BT and UDMA resins yielded copolymers and composites with the highest DCs. The significantly lower DCs of PT copolymers and their composites are attributed to the rigid aromatic core structure, tetra-vinyl functionality and limited methacrylate side-chain flexibility of the surface-active PMGDMA monomer. There was, however, an increase in the 28 d DC for the PT materials as there was for the BTHZ system. Surprisingly, the usual decrease observed in DC in going from unfilled polymer to composite was reversed for the PT system.

Effect of particle size of an amorphous calcium phosphate filler on the mechanical strength and ion release of polymeric composites.

The random clustering of amorphous calcium phosphate (ACP) particles within resin matrices is thought to diminish the strength of their polymerized composites. The objective of this study was to elucidate the effect of ball-milling on the particle size distribution (PSD) of ACP fillers and assess if improved dispersion of milled ACP in methacrylate resin sufficiently enhanced filler/matrix interactions to result in improved biaxial flexure strength (BFS), without compromising the remineralizing potential of the composites. Unmilled and wet-milled zirconia-hybridized ACP (Zr-ACP) fillers were characterized by PSD analysis, X-ray diffraction, thermogravimetric and chemical analysis, infrared spectroscopy, and scanning electron microscopy. Composite specimens made from a photoactivated, ternary methacrylate resin admixed with a mass fraction of 40% of un-milled or milled Zr-ACP were evaluated for the BFS (dry and wet) and for the release of calcium and phosphate ions into saline solutions. While having no apparent effect on the structure, composition, and morphology/topology of the fillers, milling significantly reduced the average size of Zr-ACP particulates (median diameter, d(m) = 0.9 +/- 0.2 microm) and the spread of their PSD. Better dispersion of milled Zr-ACP in the resins resulted in the improved BFS of the composites, even after aqueous soaking, and also gave a satisfactory ion release profile. The demonstrated improvement in the mechanical stability of anti-demineralizing/remineralizing ACP composites based on milled Zr-ACP filler may be beneficial in potentially extending their dental utility.

Dental composites based on amorphous calcium phosphate - resin composition/physicochemical properties study.

This study explores how the resin composition/structure affects the physicochemical properties of copolymers and their amorphous calcium phosphate (ACP)-filled composites. A series of photo-polymerizable binary and ternary matrices are formulated utilizing 2,2-bis[ p-(2(')-hydroxy-3(')methacryloxypropoxy)phenyl]propane, 2,2-bis[ p-(2(')-methacryloxypropoxy)phenyl]-propane (EBPADMA), or a urethane dimethacrylate as base monomers, and triethylene glycol dimethacrylate or hexamethylene dimethacrylate (HmDMA) with or without 2-hydroxyethyl methacrylate (HEMA) as diluent monomer. Unfilled copolymers and composites filled with 40% by mass zirconia-hybridized ACP are evaluated for biaxial flexure strength (BFS), degree of conversion (DC), mineral ion release, polymerization shrinkage (PS), and water sorption (WS). The average DC values are 82-94% and 74-91% for copolymers and composites, respectively. Unrelated to the resin composition, the PS values of composites are up to 8.4 vol. % and the BFS values of wet composite specimens are on average 51 +/- 8 MPa. The maximum WS values attained in copolymers and composites reach 4.8 mass%. Inclusion of hydrophobic HmDMA monomer in the matrices significantly reduces the WS. The levels of Ca and PO(4) released from all types of composites are significantly above the minimum necessary for the re-deposition of apatite to occur. Elevated Ca, and to a lesser extent PO(4) release, is observed in HEMA-containing, ternary EBPADMA formulations. Further resin reformulations may be needed to improve the PS of composite specimens. Poor dispersion of ;as-synthesized' ACP within the composite contributes to their inferior mechanical performance.

Amorphous calcium phosphate composites with improved mechanical properties.

Hybridized zirconium amorphous calcium phosphate (ACP)-filled methacrylate composites make good calcium and phosphate releasing materials for anti-demineralizing/remineralizing applications with low mechanical demands. The objective of this study was to assess the effect of the particle size of the filler on the mechanical properties of these composites. Photo-curable resins were formulated from ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate. Camphorquinone and ethyl-4-N,N-dimethylaminobenzoate were utilized as components of the photoinitiator system. After 2 h of mechanical milling in isopropanol, an approximate 64 % reduction in the median particle diameter was observed [27.48 µm vs. 9.98 µm] for unmilled and milled wet ACP, respectively. Dry ACP showed a 43 % reduction in particle size from pre- to post-milling. As well as dry composites, those that had been immersed in aqueous media were evaluated for their Young's Modulus, water sorption, biaxial tensile, three-point flexural and diametral tensile strength. Mechanically milling the filler increased the volume of fine particles in the composite specimens, resulting in a more homogeneous intra-composite distribution of ACP and a reduction in voids. In turn, less water diffused into the milled composites upon aqueous exposure, and they showed a marked improvement in biaxial flexure strength and a moderate improvement in flexural strength over composites with unmilled ACP. The demonstrated improvement in the mechanical stability of milled Zr-ACP composites may help in extending their dental applicability.